Ethanol → Aniline

HRID 1633979Notes

Reaction equation

HRID 1633979 reaction equation
[C:1]1(=O)[CH2:6][CH2:5][CH2:4][CH2:3][CH2:2]1.[NH2:8][C:9]1[CH:14]=[CH:13][CH:12]=[CH:11][CH:10]=1.C(O)C.[OH-].[Na+]>Cl.C(OCC)(=O)C>[C:1]1([C:12]2[CH:13]=[CH:14][C:9]([NH2:8])=[CH:10][CH:11]=2)[CH2:6][CH2:5][CH2:4][CH2:3][CH:2]=1.[NH2:8][C:9]1[CH:14]=[CH:13][CH:12]=[CH:11][CH:10]=1

Participants

8

Reactant 4

HCID 702EthanolHCID 6115AnilineHCID 7967CyclohexanoneHCID 14798Sodium Hydroxide

Product 2

HCID 6115AnilineHCID 126688602',3',4',5'-Tetrahydro-[1,1'-biphenyl]-4-amine

Reagents, catalysts & solvents 2

HCID 313Hydrochloric AcidSolventHCID 8857Ethyl AcetateSolvent

Conditions

Temperature
110 °C

Procedure

A mixture of cyclohexanone (50 g, 0.325 mol), and aniline (95 g, 1 mol) in 12 M HCl (100 mL), and ethanol (15 mL) was refluxed at 110° C. for four days. The solution was cooled and diluted with ethyl acetate. The aqueous layer was basified with 6 M NaOH. The organic layer was separate and washed with brine (3×), dried over MgSO4, and concentrated to give a brown oil. Approximately half of the crude product was introduced into a silica gel column and eluted with 5% ethyl acetate/hexane to obtain the desired product along with aniline. The combined organic fractions were extracted with 1 N HCl and separated. Addition of brine to the aqueous layer precipitated the 4-cyclohex-1-enylaniline as a cream colored solid (9 g).

Workup

  1. temperatureThe solution was cooled
  2. customThe organic layer was separate
  3. washwashed with brine (3×)
  4. dry with materialdried over MgSO4
  5. concentrationconcentrated
  6. customto give a brown oil
  7. washeluted with 5% ethyl acetate/hexane

Sources & evidence

ORD record
ord-ae85ca11030d4b35a9e0bc0cc26f837d
Source dataset
uspto-grants-2003_01
Patent number
US06503949B1

Reaction notes

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